US2668161A - Preservation of butadiene copolymers - Google Patents
Preservation of butadiene copolymers Download PDFInfo
- Publication number
- US2668161A US2668161A US256359A US25635951A US2668161A US 2668161 A US2668161 A US 2668161A US 256359 A US256359 A US 256359A US 25635951 A US25635951 A US 25635951A US 2668161 A US2668161 A US 2668161A
- Authority
- US
- United States
- Prior art keywords
- styrene
- weight
- hydroxy
- butadiene
- biphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 title claims description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title description 16
- 238000004321 preservation Methods 0.000 title description 2
- 239000004816 latex Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- IQMISEWMYIGMAH-UHFFFAOYSA-N 2-phenyl-6-(2-phenylethyl)phenol Chemical compound C1=CC=C(C=2C=CC=CC=2)C(O)=C1CCC1=CC=CC=C1 IQMISEWMYIGMAH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 46
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 235000010292 orthophenyl phenol Nutrition 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000006178 methyl benzyl group Chemical group 0.000 description 3
- 239000004306 orthophenyl phenol Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 vinyl aromatic compounds Chemical class 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
- DBUJFULDVAZULB-UHFFFAOYSA-N 1-methoxypentane Chemical compound CCCCCOC DBUJFULDVAZULB-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- YQUDMNIUBTXLSX-UHFFFAOYSA-N 2-ethenyl-5-ethylpyridine Chemical compound CCC1=CC=C(C=C)N=C1 YQUDMNIUBTXLSX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YOQXWFAPUCIKIH-UHFFFAOYSA-N 5-ethenyl-2-ethylpyridine Chemical compound CCC1=CC=C(C=C)C=N1 YOQXWFAPUCIKIH-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Definitions
- This invention relates to new and-l useful compositions of matter and to methodsY of making the same. More particularly it relates to stabilized copolymers of butadiene and styrene.
- An object of Athe invention is to provide a new class of nondiscoloring antioxidants for the copolymer rubber known as GR-S.
- a further object is to ⁇ provide a class of antioxidants suitable for adding directly to latex obtained by the emulsion copolymerization of butadiene and styrene.
- a still further object is to provide a class of materials which prevent continuedpolymerization of butadiene-styrene copolymers andv inhibit the deleterious eiects of oxygen, heat and light.
- the new stabilizers may be represented 'by the.
- the catalyst isprefera'bly employed in the form of an addition compound" with an oxygen containing organic compound.
- the preparation is conveniently carried out in' the liquid phase in making theV mono-aralk-yl derivatives of 2- and TS1-hydroxy biphenyl, how-- ever, ⁇ where desirable anfinert solvent may be employed. In preparing the monofaralkyl.
- the: crude aralkylated mixture may be Washed with ⁇ an aqueous .alkaline solution 2 inV order to remove the ⁇ catalyst and the desired productsseparated, for example by fractionaldis.
- the products are generallyviscous high boiling ⁇ pale yellow to water-white liquids although some are resinous or crystalline. They are substan-f tially insoluble in water' but have some solubility in dilute aqueous caustic soda and ink most or; While eli'cient stabilizers of.
- stabilizers the following are illustrativev but in.
- Example 1 46 parts by Weight of a boron trifluoride-phenol catalyst complex which contained 26.5% boron trifluoride -by Weight and believed to consist of a molar ratio of l of boron trilluoride to 2 oi? phenol as described by Sowa et al., J. A. C. NS. 55, ⁇ p'. 3404, 1933, was intimately mixed with 350 parts' by weight (substantially 2.05 mols) of 2-hydroxy biphenyl in a suitable reaction vessel at about Was added over a period of about one hour 368 parts by weight (substantially 60 C.
- Example 2 To a mixture of 600 parts by weight (substantially 3.52 mols) of 2-hydroxy biphenyl and 368 parts by weight (substantially 3.52 mols) of styrene was added slowly 25.5 parts by weight of a boron trifluoride-di-ethyl ether complex which possessed a boiling point of about 126 C. and contained about 48% by weight boron triuoride, the remainder being di-ethyl ether. During the addition of the catalyst which began at about C. the temperature rose momentarily to 122 C. and then dropped to about 52 C. Upon completion of the catalyst addition the mix was heated for two hours at 65-70 C. with constant agitation.
- Example 3 Into a glass or glass-lined container of suitable capacity was charged 340 parts by weight of ortho phenyl phenol (substantially 2 mols). 1.2 parts by weight of concentrated hydrochloric acid was added and the mixture heated and stirred at about 140 C. while 208 parts by weight (substantially 2 mols) of styrene was added. The styrene was added over a period of about thirty minutes while heating and stirring at 140160 C. Heating was then continued at 165-170 C. for an additional thirty minutes and the mass cooled, 5 parts by weight of aqueous sodium hydroxide added and the mixture stirred for a few minutes and cooled to room temperature. The reaction mixture was Washed with hot water and nally fractionally distilled. 611.2 parts by weight or about 18.9% theory of a product having a boiling point of 192 0./3 mm. was obtained. IThis product is believed to be 2-hydroxy-3(a methyl benzyl) biphenyl.
- Example 4 Approximately 0.5 part of concentrated hydrochloric acid was added to 340 parts by weight (substantially 2 mols) of ortho phenyl phenol and the mixture heated to a temperature of 120-130 C. 104 parts by weight (substantially 1 mol) of styrene was then added gradually over a period of forty to forty-nve minutes while stirring and heating at 120130 C. and stirring and heating then continued for another thirty minutes. The reaction mixture was then cooled, neutralized with aqueous sodium hydroxide and fractionated. In this manner there was isolated about 4.6% yield of the same product as described in Example 3, boiling at approximately 194 C /2 mm.
- catalysts than those specifically described may be employed as well, for example the 4 boron trifluoride complexes with respectively dimethyl ether (boiling point about 127 C.) ethyl methyl ether (boiling point about 127 CJ, diisopropyl ether (melting point about 68 C.) amyl methyl ether (melting point about 41 C.), anisole, phenetole, phenyl ethyl ether, phenyl methyl ether, tetrahydrofuran (melting point about 9 C.), ethylene oxide, and the like.
- oxygen containing organic compounds which combine with boron triuoride to form catalyst complexes thanV the preferred ether complexes which successfully aid in the production of the new monoaralkylated products are the alcohols e. g. methanol, ethanol, isopropanol, glycol, ethylene chlorohydrin, the cresols, ete), the esters (e. g. the methyl and ethyl esters of monobasic aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid, crotonic acid, chloracetic acid and the esters of benzoic acid, oxalic acid, maleic acid, succinic acid, eta), the acids (e. g.
- Arnides and oximes also form boron trifluoride addition compounds which exhibit similar catalytic activity, as for example, acetamide, propionamide, and the like.
- the new materials are eifective in retarding polymerization during operations subsequent to cessation of the emulsion polymerization of butadiene and styrene, i. e., they retard cross linking or chain growth during the stripping and blowing down operations employed to remove the unreacted monomers.
- the emulsion polymerization of butadiene and styrene is carried out to about 70-30% usually and chemicals whose function is to prevent further polymerization are called short stops.
- two identical butadiene-1,3-styrene emulsion polymerization systems were prepared. The polymerization was then carried out over a period of about 16 hours under identical reaction conditions.
- copolymer of the untreated system was less soluble in benzene than the treated copolymer, thus indicating that crosslinking or chain growth was retarded by the presence of the di-aralkylated hydroxy biphenyl. Substantially no increase in yield of copolymer was noted in the treated system after the 5 hour additional agitation period whereas the percent conversion increased about 5% in the untreated system.
- the new products may be incorporated by addition in liquid form or in 4emulsion to the solid synthetic rubber during the milling operation or to a latex containing the synthetic rubber dispersed in an aqueous medium such as that ordinarily obtained by an emulsion polymerization process.
- the preferred method of introducing the new stabilizers is to add the material to the latex before or during coagulation. Consequently, the new stabilizers are homogeneously incorporated Within the synthetic rubber such that the rubber is obtained in a stabilized state. Small amounts, as for example 0.25 to 5% based upon the rubber have been found most effective, however amounts outside this range may be employed.
- the synthetic rubbers having incorporated therein the new products for example reaction products of two molecular proportions of styrene and one molecular proportion of a hydroxy biphenyl, exhibited good plasticity and the rubber-like copolymers neither discolored upon exposure to light nor hardened due to heat.
- the invention is applicable to the protection of copolymers of conjugated dienes and vinyl aromatic compounds.
- Suitable examples of the former are 1,3-butadiene, isoprene, 2-cyanobutadiene-1,3, cyclopentadiene1,3, piperylene, dimethyl butadiene1,3 and 2-methy1-l,3penta diene.
- Vinyl aromatic compounds which may be employed include styrene, a methyl styrene, monochloro styrene, dichloro styrene, Vinyl naphthalene, vinyl biphenyl, vinyl carbazole, 2- vinyl-5-ethyl pyridine and 2-ethyl-5-vinyl pyridine.
Description
Patented Feb. 2, l`954 PRESERVATION F BUTADIENE COPOLYMERS David J Beaver.Richmond Heights, Mo., assigner to Monsanto Chemical Company, St. Louis, Mo., y acorporation of Delaware No Drawing. Application November 14, 1951;, Serial No. 256,359
8-Claims. (Cl. 260-45.95)
This invention relates to new and-l useful compositions of matter and to methodsY of making the same. More particularly it relates to stabilized copolymers of butadiene and styrene.
An object of Athe invention is to provide a new class of nondiscoloring antioxidants for the copolymer rubber known as GR-S. A further object is to` provide a class of antioxidants suitable for adding directly to latex obtained by the emulsion copolymerization of butadiene and styrene. A still further object is to provide a class of materials which prevent continuedpolymerization of butadiene-styrene copolymers andv inhibit the deleterious eiects of oxygen, heat and light. Other and further objects, will in part be. apparent and .in part particularly pointed out in the description following.
It has been found that these and other objects are achieved by treating. copolymers. of butadiene and styrene with an aralkylated hydroxy bi.- phenyl.
The new stabilizers may be represented 'by the.
general vformula example, styrene, oand p-chlor styrene, o, m-,.
and p-methyl styrene, o, mandv p-lethyl styrene, p-tert. butyl styrene; and the like, withl a hydroxy biphenyll in the presence of a boron triiluoride catalyst. The catalyst .isprefera'bly employed in the form of an addition compound" with an oxygen containing organic compound. The preparation is conveniently carried out in' the liquid phase in making theV mono-aralk-yl derivatives of 2- and TS1-hydroxy biphenyl, how-- ever,` where desirable anfinert solvent may be employed. In preparing the monofaralkyl. .de-f rivatives of 4-,hydroxy biphenyl itis preferable to employ an inert solvent, Upon completionofv the reaction the: crude aralkylated mixture may be Washed with` an aqueous .alkaline solution 2 inV order to remove the `catalyst and the desired productsseparated, for example by fractionaldis.-
tillation.- Reaction temperatures of about e' C. have been found most advantageous, how-.f
ever, depending upon the reactants and whether or not an inert solvent is used higher or flower temperatures may be employed.
The products are generallyviscous high boiling` pale yellow to water-white liquids although some are resinous or crystalline. They are substan-f tially insoluble in water' but have some solubility in dilute aqueous caustic soda and ink most or; While eli'cient stabilizers of.
stabilizers the following are illustrativev but in.
nowise limitative of the invention.
Example 1 46 parts by Weight of a boron trifluoride-phenol catalyst complex which contained 26.5% boron trifluoride -by Weight and believed to consist of a molar ratio of l of boron trilluoride to 2 oi? phenol as described by Sowa et al., J. A. C. NS. 55,` p'. 3404, 1933, was intimately mixed with 350 parts' by weight (substantially 2.05 mols) of 2-hydroxy biphenyl in a suitable reaction vessel at about Was added over a period of about one hour 368 parts by weight (substantially 60 C. To the melt 3.52 mols) of styrene with agitation while retain'- ing the temperature at about 58%59o C. Upon completion of the styrene addition the mix was; C. for a period of thirty 90 parts by Weight of a 25% caustic: solution was stirred into the reaction mix and heated at about 70 minutes.
the composite washed' several times with hot water to remove the boron truorideeatalyst and subsequently fractonally distilled. About 62` parts by weight' of unreacted 2-hydroxy biphenyl Was recovered and approximately 1187r Weight of a resinous material believed to styrene was separated lout mix. Approximately %A biphenyls. .Upon refract'ionatingA the latter there Water-white viscous one belieyeell to be 2-hydroxy-3 (a methyibenzynbipuenyi have 0./2 min.; a speeicfA was obtained principally two liquid mono aralkylated products,
ins. a 'boiling' point ofl. 1'9'4 gravity of 1.089 at 25A C. and an N'D of 41,6193 at 25 C., and the other believed to be-'2fhydroxy dite-methyl benzyl) .bphenylhaving a boilingA Darts rbybe Poly- Vof vthe Acrude reaction- 0f ythe original harge Was isolated as a pale yellow viscous liquid iden;- tied as al mixture of. mono aralkylated-2-hydroxyf point of 255258 C./2 mm., a specific gravity of 1.097 at 25 C. and an ND of 1.6190 at 25 C. Determination of the hydroxyl number of the latter by the Zerewitinoif method gave 4.6% hydroxy groups as compared to the calculated value of 4.5%. The figure for the former product was 6.5% hydroxygroups as compared to a calculated value of 6.2%.
Example 2 To a mixture of 600 parts by weight (substantially 3.52 mols) of 2-hydroxy biphenyl and 368 parts by weight (substantially 3.52 mols) of styrene was added slowly 25.5 parts by weight of a boron trifluoride-di-ethyl ether complex which possessed a boiling point of about 126 C. and contained about 48% by weight boron triuoride, the remainder being di-ethyl ether. During the addition of the catalyst which began at about C. the temperature rose momentarily to 122 C. and then dropped to about 52 C. Upon completion of the catalyst addition the mix was heated for two hours at 65-70 C. with constant agitation. Thereupon the mix was Washed with a hot aqueous caustic soda solution and subsequently with hot water to remove the catalyst and finally fractionally distilled. After removal of the unreacted 2-hydroxy biphenyl and a tarry residue believed to be polystyrene, approximately 377 parts by Weight of a water-white viscous liquid identiied as an aralkylated 2-hydroxy biphenyl of which the principal component was found to be the high boiling product of Example l which was believed to be 2-hydroxy-di(a methyl benzyl) biphenyl. l
Example 3 Into a glass or glass-lined container of suitable capacity was charged 340 parts by weight of ortho phenyl phenol (substantially 2 mols). 1.2 parts by weight of concentrated hydrochloric acid was added and the mixture heated and stirred at about 140 C. while 208 parts by weight (substantially 2 mols) of styrene was added. The styrene was added over a period of about thirty minutes while heating and stirring at 140160 C. Heating was then continued at 165-170 C. for an additional thirty minutes and the mass cooled, 5 parts by weight of aqueous sodium hydroxide added and the mixture stirred for a few minutes and cooled to room temperature. The reaction mixture was Washed with hot water and nally fractionally distilled. 611.2 parts by weight or about 18.9% theory of a product having a boiling point of 192 0./3 mm. was obtained. IThis product is believed to be 2-hydroxy-3(a methyl benzyl) biphenyl.
Example 4 Approximately 0.5 part of concentrated hydrochloric acid was added to 340 parts by weight (substantially 2 mols) of ortho phenyl phenol and the mixture heated to a temperature of 120-130 C. 104 parts by weight (substantially 1 mol) of styrene was then added gradually over a period of forty to forty-nve minutes while stirring and heating at 120130 C. and stirring and heating then continued for another thirty minutes. The reaction mixture was then cooled, neutralized with aqueous sodium hydroxide and fractionated. In this manner there was isolated about 4.6% yield of the same product as described in Example 3, boiling at approximately 194 C /2 mm.
Other catalysts than those specifically described may be employed as well, for example the 4 boron trifluoride complexes with respectively dimethyl ether (boiling point about 127 C.) ethyl methyl ether (boiling point about 127 CJ, diisopropyl ether (melting point about 68 C.) amyl methyl ether (melting point about 41 C.), anisole, phenetole, phenyl ethyl ether, phenyl methyl ether, tetrahydrofuran (melting point about 9 C.), ethylene oxide, and the like. Other oxygen containing organic compounds which combine with boron triuoride to form catalyst complexes thanV the preferred ether complexes which successfully aid in the production of the new monoaralkylated products are the alcohols e. g. methanol, ethanol, isopropanol, glycol, ethylene chlorohydrin, the cresols, ete), the esters (e. g. the methyl and ethyl esters of monobasic aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid, crotonic acid, chloracetic acid and the esters of benzoic acid, oxalic acid, maleic acid, succinic acid, eta), the acids (e. g. formic, acetic, propionic, butyric. benzoic, glycolic, maleic, crotonic, lactic, oleic, oxalic, succinic, chloracetic, etc., and the anhydrides thereof), the aldehydes (e. g. acetaldehyde, trimethyl acetaldehyde, benzaldehyde) and the ketones (e. g. acetone, acetophenone). Arnides and oximes also form boron trifluoride addition compounds which exhibit similar catalytic activity, as for example, acetamide, propionamide, and the like.
The new materials are eifective in retarding polymerization during operations subsequent to cessation of the emulsion polymerization of butadiene and styrene, i. e., they retard cross linking or chain growth during the stripping and blowing down operations employed to remove the unreacted monomers. The emulsion polymerization of butadiene and styrene is carried out to about 70-30% usually and chemicals whose function is to prevent further polymerization are called short stops. As exemplary of the short stopping activity of the new compounds two identical butadiene-1,3-styrene emulsion polymerization systems were prepared. The polymerization was then carried out over a period of about 16 hours under identical reaction conditions. One system Was then treated with an aqueous emulsion containing approximately 0.3% by weight based upon the original total monomer charge of the product of Example 2, believed to be 2-hydroxy-di(a methyl benzyl) biphenyl while the other system received no treatment. Agitation of the two systems was then continued at room temperature for about 5 hours. Thereupon the copolymers were coagulated and recovered in the usual manner. The copolymer treated with the di-aralkylated hydroxy biphenyl was soft and plastic whereas the product of the untreated system was hard and tough. The copolymer of the untreated system was less soluble in benzene than the treated copolymer, thus indicating that crosslinking or chain growth was retarded by the presence of the di-aralkylated hydroxy biphenyl. Substantially no increase in yield of copolymer was noted in the treated system after the 5 hour additional agitation period whereas the percent conversion increased about 5% in the untreated system.
As stabilizers for the rubber-like copolymer of butadiene-1,3 and styrene the new products may be incorporated by addition in liquid form or in 4emulsion to the solid synthetic rubber during the milling operation or to a latex containing the synthetic rubber dispersed in an aqueous medium such as that ordinarily obtained by an emulsion polymerization process.
The preferred method of introducing the new stabilizers is to add the material to the latex before or during coagulation. Consequently, the new stabilizers are homogeneously incorporated Within the synthetic rubber such that the rubber is obtained in a stabilized state. Small amounts, as for example 0.25 to 5% based upon the rubber have been found most effective, however amounts outside this range may be employed. The synthetic rubbers having incorporated therein the new products, for example reaction products of two molecular proportions of styrene and one molecular proportion of a hydroxy biphenyl, exhibited good plasticity and the rubber-like copolymers neither discolored upon exposure to light nor hardened due to heat. Other tests showed that the mixtures of reactants obtained by condensing ortho phenyl phenol with styrene and distilling 01T unreacted constituents were eiective antioxidants for GR-S latex. Thus, the crude mixture obtained as a residue after topping the reaction mixture is an eflicient antioxidant suitable for addition to the latex obtained by the emulsion polymerization of butadiene and styrene.
The invention is applicable to the protection of copolymers of conjugated dienes and vinyl aromatic compounds. Suitable examples of the former are 1,3-butadiene, isoprene, 2-cyanobutadiene-1,3, cyclopentadiene1,3, piperylene, dimethyl butadiene1,3 and 2-methy1-l,3penta diene. Vinyl aromatic compounds which may be employed include styrene, a methyl styrene, monochloro styrene, dichloro styrene, Vinyl naphthalene, vinyl biphenyl, vinyl carbazole, 2- vinyl-5-ethyl pyridine and 2-ethyl-5-vinyl pyridine.
This application is a continuation-in-part of copending application Serial No. 120,599 led October 10, 1949.
What is claimed is:
1. The process of stabilizing a rubber-like copolymer of a conjugated diene monomer and a vinyl aromatic monomer which comprises adding to the latex resulting from the emulsion copolymerization thereof a small amount of a phenethyl hydroxy biphenyl of the structure where n is an integer less than three.
3. 'Ihe process of stabilizing a rubber-like copolymer of butadiene-1,3 and styrene which comprises adding to the latex resulting from the emulsion copolymerization thereof a small amount of a phenethyl hydroxy biphenyl of the structure i {Qt} -O where n is an integer less than three.
4. The process of stabilizing a rubber-like copolymer of butadiene-1,3 and styrene which comprises adding to the latex resulting from the emulsion copolymerization thereof a small amount of a phenethyl hydroxy biphenyl of the structure Y 5. A rubber-like copolymer of a conjugated diene monomer and a vinyl aromatic monomer having incorporated therein a small amount of a phenethyl hydroxy biphenyl of the structure @SEQ/Rl [Gil where n is an integer less than three.
7. A rubber-like copolymer of Ibutadiene-1,3 and styrene having incorporated therein a small amount of a phenethyl hydroxy biphenyl of the structure [on o@ Where n is an integer less than three.
8. A rubber-like copolymer of butadiene-1,3 and styrene having incorporated therein a small amount of a phenethyl hydroxy biphenyl of the No references cited.
DAVID J. BEAVER.
Claims (1)
1. THE PROCESS OF STABILIZING A RUBBER-LIKE COPOLYMER OF A CONJUGATED DIENE MONOMER AND A VINYL AROMATIC MONOMER WHICH COMPRISES ADDING TO THE LATEX RESULTING FROM THE EMULSION COPOLYMERIZATION THEREOF A SMALL AMOUNT OF A PHENETHYL HYDROXY BIPHENYL OF THE STRUCTURE
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US256359A US2668161A (en) | 1951-11-14 | 1951-11-14 | Preservation of butadiene copolymers |
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US256359A US2668161A (en) | 1951-11-14 | 1951-11-14 | Preservation of butadiene copolymers |
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US2668161A true US2668161A (en) | 1954-02-02 |
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US256359A Expired - Lifetime US2668161A (en) | 1951-11-14 | 1951-11-14 | Preservation of butadiene copolymers |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2883364A (en) * | 1955-03-01 | 1959-04-21 | Goodrich Co B F | Stabilization of rubber with resinous bis-cresols |
US3153098A (en) * | 1959-05-28 | 1964-10-13 | Ethyl Corp | Bis phenols |
-
1951
- 1951-11-14 US US256359A patent/US2668161A/en not_active Expired - Lifetime
Non-Patent Citations (1)
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2883364A (en) * | 1955-03-01 | 1959-04-21 | Goodrich Co B F | Stabilization of rubber with resinous bis-cresols |
US3153098A (en) * | 1959-05-28 | 1964-10-13 | Ethyl Corp | Bis phenols |
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